JP3845977B2 - Method for producing 4,4'-bischloromethylbiphenyl - Google Patents
Method for producing 4,4'-bischloromethylbiphenyl Download PDFInfo
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- JP3845977B2 JP3845977B2 JP24880097A JP24880097A JP3845977B2 JP 3845977 B2 JP3845977 B2 JP 3845977B2 JP 24880097 A JP24880097 A JP 24880097A JP 24880097 A JP24880097 A JP 24880097A JP 3845977 B2 JP3845977 B2 JP 3845977B2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P20/00—Technologies relating to chemical industry
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Description
【０００１】
【発明の属する技術分野】
本発明は、蛍光増白剤やエポキシ樹脂原料などの合成中間体として有用な化合物である４，４’−ビスクロロメチルビフェニルの製造法に関する。
【０００２】
【従来の技術】
従来のビフェニルを塩化亜鉛の存在下にクロロメチル化して４，４’−ビスクロロメチルビフェニルを製造する方法としては、（１）水、塩化亜鉛ならびに低級脂肪族カルボン酸からなる触媒系の存在下において、ビフェニルをホルムアルデヒド及び塩化水素と反応させる方法（特公昭４０−３７７４号公報）、（２）ビフェニルをシクロヘキサン溶媒中でパラホルムアルデヒド及び塩化水素と反応させる方法（特公昭４６−２９９０８号公報）、（３）ビフェニルをホルムアルデヒド重合物及び塩化チオニルと反応させる方法（特開平３−１８８０２９号公報）が知られている。
【０００３】
しかしながら、（１）の方法では、触媒として使用する塩化亜鉛と低級脂肪酸カルボン酸の使用量が多く、工業的に実施するためには循環して使用することが望ましいが、反応開始時の水の濃度が収率に大きく影響するため、反応により生成する水を反応系より除去する必要があり、水の除去に非常に煩雑な操作が必要となる問題がある。（２）の方法では、触媒使用量は少ないが、反応時間が２４時間と長いため生産性に問題がある。（３）の方法では、反応時間が比較的短いものの高価な塩化チオニルを多量に使用する必要があることから、副生するイオウ化合物の処理なども含め、経済性に問題があった。
【０００４】
【発明が解決しようとする課題】
前記のような技術背景に鑑み、本発明は、ビフェニルをクロロメチル化して４，４’−ビスクロロメチルビフェニルを製造する方法において、４，４’−ビスクロロメチルビフェニルを少ない触媒量で、短時間にかつ高収率で製造することができ、イオウ化合物を副生しない経済的な製造法を提供することを課題とする。
【０００５】
【課題を解決するための手段】
本発明者らは、前記の公知の製法における問題点を改良すべく、鋭意検討した結果、脂肪酸無水物又は脂肪酸塩化物を添加して、常圧又は加圧下に、反応を行うことにより、４，４’−ビスクロロメチルビフェニルを高収率で製造できると共に、前記の課題を全て解決できることを見いだした。
即ち、本発明の課題は、ビフェニルを塩化亜鉛の存在下にホルムアルデヒド重合物及び塩化水素と反応させて４，４’−ビスクロロメチルビフェニルを製造するに当たり、脂肪酸無水物又は脂肪酸塩化物を添加して、常圧又は加圧下に、反応を行うことを特徴とする４，４’−ビスクロロメチルビフェニルの製造法によって達成される。
【０００６】
また、本発明の課題は、好ましくは、
１）ビフェニルを塩化亜鉛の存在下にホルムアルデヒド重合物及び塩化水素と反応させて４，４’−ビスクロロメチルビフェニルを製造するに当たり、脂肪酸無水物又は脂肪酸塩化物を添加して常圧又は加圧下に、反応を行うことを特徴とする４，４’−ビスクロロメチルビフェニルの製造法において、脂肪酸無水物が無水酢酸である４，４’−ビスクロロメチルビフェニルの製造法、
２）脂肪酸塩化物が塩化アセチルである１）記載の製造法、
３）反応が０．５〜５．０Ｋｇ／ｃｍ2 の加圧下で行われる１）記載の製造法であり、これらを組合わせた製法も好ましい。
【０００７】
【発明の実施の形態】
【０００８】
本発明は、例えば以下に示すような
反応式（１）
【０００９】
【化１】
で表すことができる。
【００１１】
本発明の製法において使用するホルムアルデヒド重合物としては、例えばパラホルムアルデヒド、ポリオキシメチレン、トリオキサンなどを挙げることができ、工業的にはパラホルムアルデヒド（特に純度７５重量％以上のパラホルムアルデヒド）が好ましい。
ホルムアルデヒド重合物の使用量としては、通常ビフェニル１モルに対して１．８〜３．０倍モル、好ましくは２．０〜２．６倍モルである。
【００１２】
本発明の製法において使用する塩化亜鉛としては、純度の高いものが好ましく、純度９０重量％以上ものが特に好ましい。
塩化亜鉛の使用量としては、通常ビフェニル１モルに対して０．３〜１．０倍モル、好ましくは０．５〜０．８倍モルである。
【００１３】
本発明の製法において使用する塩化水素の使用量としては、通常ビフェニル１モルに対して１．８〜５０倍モル、好ましくは２．０〜３０倍モルである。
【００１４】
本発明の製法において使用する脂肪酸無水物としては、例えば無水酢酸、無水コハク酸、無水マレイン酸などを挙げることができ、好ましくは無水酢酸である。
本発明の製法において使用する脂肪酸塩化物としては、例えば塩化アセチル、塩化プロピオニル、塩化バレロイル、オキサリルクロライドなどを挙げることができ、好ましくは塩化アセチルである。
本発明の製法において使用する脂肪酸無水物および脂肪酸塩化物は、単独又は混合しても使用できる。使用量としては、通常ビフェニル１モルに対して０．０５〜１．５倍モル、好ましくは０．１〜１．０倍モルである。
本発明の製法における脂肪酸無水物および脂肪酸塩化物の添加方法としては、他の反応に使用する化合物と一緒に仕込んでも、反応開始時又は反応途中で滴下してもよい。
【００１５】
本発明の製法において使用する反応溶媒としては、反応に不活性な溶媒であれば特に制限はないが、例えばｎ−ヘプタン、シクロヘキサン、石油系溶剤などの炭素原子数５〜２５の脂肪族炭化水素、ジクロロエタン、クロロホルム、四塩化炭素などのハロゲン置換炭化水素、酢酸、プロピオン酸などの低級脂肪酸などを挙げることができ、好ましくは脂肪族炭化水素である。これらの反応溶媒は単独又は混合しても使用できる。
反応溶媒の使用量としては、通常ビフェニルに対して０．８〜５重量倍、好ましくは１．０〜３．０重量倍モルである。
【００１６】
本発明の製法は、常圧又は加圧下に行われるが、反応速度を上げるためには０．１〜１０Ｋｇ／ｃｍ2 で反応を行うことが好ましく、０．５〜５．０Ｋｇ／ｃｍ2 で反応を行うことがより好ましい。
本発明の製法の反応温度としては、通常２０〜８０℃であり、好ましくは３０〜６０℃である。
本発明の製法の反応時間は、反応温度、触媒量および使用する反応溶媒などにより異なるが、通常５〜１２時間であり、好ましくは８〜１１時間である。
【００１７】
本発明の製法において、生成した４，４’−ビスクロロメチルビフェニルを含む反応混合物から該目的化合物を得る方法は、通常の濾過、抽出、再結晶などにより分離・精製すればよい。
【００１８】
【実施例】
以下に実施例を示して本発明をさらに詳しく説明するが、本発明の範囲はこれらに限定されるものではない。実施例および比較例における、ＧＣ純度はガスクロマトグラフィ−分析における純度（面積％）である。
【００１９】
実施例１
冷却管、温度計、ガス導入管及び攪拌機を備えた内容積３００ｍｌの４つ口フラスコに、ビフェニル４６．２５ｇ（０．３０モル）、９４重量％パラホルムアルデヒド２１．０６ｇ（０．６６モル）、９８重量％塩化亜鉛２４．５ｇ（０．１８モル）およびシクロヘキサン６０ｇを入れ、５０℃で撹拌しながら、塩化水素ガスを８０ｍｌ／ｍｉｎで導入し、撹拌しながら滴下ロ−トで無水酢酸１０ｇ（０．０９８モル）を６０分間で滴下して反応させた。滴下終了後、更に７時間塩化水素ガスを導入して反応させた。
反応終了後、得られた反応溶液のＧＣ分析による溶媒以外の組成は、未反応ビフェニルは０．１％、４，４’−ビスクロロメチルビフェニルは６８．９％であることがわかった。
反応終了後、得られた反応溶液を１５℃まで冷却した後、水１５ｍｌとシクロヘキサン６０ｍｌとを加え、撹拌したのち、吸引濾過により析出した４，４’−ビスクロロメチルビフェニルを分離した。得られた４，４’−ビスクロロメチルビフェニルを、さらにメタノ−ル１２０ｍｌで洗浄後、室温で２４時間減圧乾燥し、乾燥品５１．１ｇ（ビフェニルに対する収率＝６７．９％）を得た。乾燥品のＧＣ純度は９０．４％であった。この乾燥品をシクロヘキサンより再結晶すると、融点１３６〜１３７℃、ＧＣ純度９９．０％の白色結晶を得た。
【００２０】
実施例２
冷却管、温度計、ガス導入管及び攪拌機を備えた内容積３００ｍｌの４つ口フラスコに、ビフェニル４６．２５ｇ（０．３０モル）、９２重量％パラホルムアルデヒド２１．５２ｇ（０．６６モル）、９８重量％塩化亜鉛２４．５ｇ（０．１８モル）およびシクロヘキサン６０ｇを入れ、５０℃で撹拌しながら、塩化水素ガスを８０ｍｌ／ｍｉｎで導入し、撹拌しながら滴下ロ−トで無水酢酸２０ｇ（０．１９６モル）を４時間で滴下して反応させた。滴下終了後、更に５時間塩化水素ガスを導入して反応させた。
反応終了後、得られた反応溶液のＧＣ分析による溶媒以外の組成は、未反応ビフェニルは０．１％、４，４’−ビスクロロメチルビフェニルは６４．４％であることがわかった。
反応終了後、得られた反応溶液を１５℃まで冷却した後、水５０ｍｌとシクロヘキサン６０ｍｌとを加え、撹拌したのち、吸引濾過により析出した４，４’−ビスクロロメチルビフェニルを分離した。得られた４，４’−ビスクロロメチルビフェニルを、さらにメタノ−ル１２０ｍｌで洗浄後、室温で２４時間減圧乾燥し、乾燥品４７．４ｇ（ビフェニルに対する収率＝６２．９％）を得た。乾燥品のＧＣ純度は９２．２％であった。
【００２１】
実施例３
反応温度を４０℃とし、無水酢酸１０ｇを１時間で滴下し、滴下後の塩化水素ガス吹き込み時間を１０時間とした他は、実施例２と同様に反応させた。
反応終了後、得られた反応溶液のＧＣ分析による溶媒以外の組成は、未反応ビフェニルは０％、４，４’−ビスクロロメチルビフェニルは６３．７％であることがわかった。
【００２２】
実施例４
無水酢酸に代えてアセチルクロライド９．４５ｇ（０．１モル）を使用した他は、実施例２と同様に反応させた。
反応終了後、得られた反応溶液のＧＣ分析による溶媒以外の組成は、未反応ビフェニルは０％、４，４’−ビスクロロメチルビフェニルは６２．４％であることがわかった。
【００２３】
実施例５
温度計、ガス導入管及び攪拌機を備えた内容積３００ｍｌのガラス製オ−トクレ−ブに、ビフェニル４６．２５ｇ（０．３０モル）、９２重量％パラホルムアルデヒド２１．５２ｇ（０．６６モル）、９８重量％塩化亜鉛２４．５ｇ（０．１８モル）および無水酢酸１０ｇ（０．０９８モル）および溶媒として石油系溶剤（商品名：ＳＨＥＬＬＳＯＬ Ｄ40 Ｓｈｅｌｌ社製）を入れ、４０℃で撹拌しながら、塩化水素ガスを導入し、系内を塩化水素ガスで置換した後、ガス出口を閉鎖し、圧力を２Ｋｇ／ｃｍ2 で保ったまま、１１時間攪拌して反応させた。反応終了後、得られた反応溶液のＧＣ分析による溶媒以外の組成は、未反応ビフェニルは０．１％、４，４’−ビスクロロメチルビフェニルは６９．２％であることがわかった。
【００２４】
比較例１
無水酢酸を添加せず、塩化水素ガス吹き込み時間を１０時間とした他は、実施例２と同様に反応させた。
反応終了時の得られた反応溶液のＧＣ分析による溶媒以外の組成は、未反応ビフェニルは６．１％、４，４’−ビスクロロメチルビフェニルは３７．４％であることがわかった。
【００２５】
【発明の効果】
本発明の製法によれば、４，４’−ビスクロロメチルビフェニルを少ない触媒量で、短時間にかつ高収率で製造することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a process for producing 4,4′-bischloromethylbiphenyl, which is a compound useful as a synthetic intermediate for fluorescent brighteners and epoxy resin raw materials.
[0002]
[Prior art]
As a conventional method for producing 4,4′-bischloromethylbiphenyl by chloromethylating biphenyl in the presence of zinc chloride, (1) in the presence of a catalyst system comprising water, zinc chloride and a lower aliphatic carboxylic acid. In which biphenyl is reacted with formaldehyde and hydrogen chloride (Japanese Patent Publication No. 40-3774), (2) a method in which biphenyl is reacted with paraformaldehyde and hydrogen chloride in a cyclohexane solvent (Japanese Patent Publication No. 46-29908), (3) A method of reacting biphenyl with a formaldehyde polymer and thionyl chloride (Japanese Patent Laid-Open No. 3-1888029) is known.
[0003]
However, in the method (1), the amount of zinc chloride and lower fatty acid carboxylic acid used as the catalyst is large, and it is desirable to circulate and use it for industrial implementation. Since the concentration greatly affects the yield, it is necessary to remove water produced by the reaction from the reaction system, and there is a problem that a very complicated operation is required for removing water. In the method (2), the amount of catalyst used is small, but there is a problem in productivity because the reaction time is as long as 24 hours. In the method (3), although it is necessary to use a large amount of expensive thionyl chloride although the reaction time is relatively short, there is a problem in economy including treatment of a by-product sulfur compound.
[0004]
[Problems to be solved by the invention]
In view of the technical background as described above, the present invention provides a method for producing 4,4′-bischloromethylbiphenyl by chloromethylating biphenyl and reducing the amount of 4,4′-bischloromethylbiphenyl with a small catalytic amount. It is an object of the present invention to provide an economical production method that can be produced in a long time and in a high yield and does not produce a sulfur compound as a by-product.
[0005]
[Means for Solving the Problems]
As a result of intensive investigations aimed at improving the problems in the above-mentioned known production methods, the present inventors added a fatty acid anhydride or a fatty acid chloride, and carried out the reaction under normal pressure or under pressure, whereby 4 It was found that 4,4′-bischloromethylbiphenyl can be produced in a high yield and all the above problems can be solved.
That is, an object of the present invention is to add a fatty acid anhydride or a fatty acid chloride when producing 4,4′-bischloromethylbiphenyl by reacting biphenyl with a formaldehyde polymer and hydrogen chloride in the presence of zinc chloride. Thus, this is achieved by a process for producing 4,4′-bischloromethylbiphenyl characterized by carrying out the reaction under normal pressure or under pressure.
[0006]
The subject of the present invention is preferably
1) In producing 4,4′-bischloromethylbiphenyl by reacting biphenyl with formaldehyde polymer and hydrogen chloride in the presence of zinc chloride, fatty acid anhydride or fatty acid chloride is added under normal pressure or pressure. And a process for producing 4,4′-bischloromethylbiphenyl, wherein the fatty acid anhydride is acetic anhydride,
2) The production method according to 1), wherein the fatty acid chloride is acetyl chloride,
3) The production method according to 1), wherein the reaction is carried out under a pressure of 0.5 to 5.0 kg / cm 2 , and a production method combining these is also preferred.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
[0008]
The present invention provides a reaction formula (1) as shown below, for example.
[0009]
[Chemical 1]
Can be expressed as
[0011]
Examples of the formaldehyde polymer used in the production method of the present invention include paraformaldehyde, polyoxymethylene, trioxane and the like, and industrially paraformaldehyde (particularly paraformaldehyde having a purity of 75% by weight or more) is preferable.
The amount of formaldehyde polymer used is usually 1.8 to 3.0 times mol, preferably 2.0 to 2.6 times mol for 1 mol of biphenyl.
[0012]
The zinc chloride used in the production method of the present invention preferably has a high purity, and particularly preferably has a purity of 90% by weight or more.
The amount of zinc chloride used is usually 0.3 to 1.0 times mol, preferably 0.5 to 0.8 times mol for 1 mol of biphenyl.
[0013]
The amount of hydrogen chloride used in the production method of the present invention is usually 1.8 to 50 times mol, preferably 2.0 to 30 times mol for 1 mol of biphenyl.
[0014]
Examples of the fatty acid anhydride used in the production method of the present invention include acetic anhydride, succinic anhydride, maleic anhydride and the like, preferably acetic anhydride.
Examples of the fatty acid chloride used in the production method of the present invention include acetyl chloride, propionyl chloride, valeroyl chloride, oxalyl chloride, and the like, and preferably acetyl chloride.
The fatty acid anhydride and fatty acid chloride used in the production method of the present invention can be used alone or in combination. As a usage-amount, it is 0.05-1.5 times mole normally with respect to 1 mol of biphenyl, Preferably it is 0.1-1.0 times mole.
As a method for adding the fatty acid anhydride and the fatty acid chloride in the production method of the present invention, the fatty acid anhydride and the fatty acid chloride may be added together with a compound used for another reaction, or may be dropped at the start of the reaction or during the reaction.
[0015]
The reaction solvent used in the production method of the present invention is not particularly limited as long as it is an inert solvent for the reaction, but for example, an aliphatic hydrocarbon having 5 to 25 carbon atoms such as n-heptane, cyclohexane, petroleum solvent and the like. , Halogen-substituted hydrocarbons such as dichloroethane, chloroform and carbon tetrachloride, lower fatty acids such as acetic acid and propionic acid, and the like, preferably aliphatic hydrocarbons. These reaction solvents can be used alone or in combination.
The amount of the reaction solvent used is usually 0.8 to 5 times by weight, preferably 1.0 to 3.0 times by mole, relative to biphenyl.
[0016]
The process of the present invention is atmospheric pressure or carried out under pressure, in order to increase the reaction rate is preferably to carry out the reaction in 0.1 to 10 / cm 2, at 0.5~5.0Kg / cm 2 It is more preferable to carry out the reaction.
As reaction temperature of the manufacturing method of this invention, it is 20-80 degreeC normally, Preferably it is 30-60 degreeC.
Although the reaction time of the manufacturing method of this invention changes with reaction temperature, the amount of catalysts, the reaction solvent to be used, etc., it is 5 to 12 hours normally, Preferably it is 8 to 11 hours.
[0017]
In the production method of the present invention, a method for obtaining the target compound from the reaction mixture containing 4,4′-bischloromethylbiphenyl thus produced may be separated and purified by ordinary filtration, extraction, recrystallization and the like.
[0018]
【Example】
The present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to these examples. The GC purity in Examples and Comparative Examples is the purity (area%) in gas chromatography analysis.
[0019]
Example 1
In a four-necked flask having an internal volume of 300 ml equipped with a condenser, a thermometer, a gas inlet tube and a stirrer, 46.25 g (0.30 mol) of biphenyl, 21.06 g (0.66 mol) of 94 wt% paraformaldehyde, 24.5 g (0.18 mol) of 98 wt% zinc chloride and 60 g of cyclohexane were added, hydrogen chloride gas was introduced at 80 ml / min while stirring at 50 ° C., and 10 g of acetic anhydride was added with stirring at a dropping funnel. 0.098 mol) was added dropwise over 60 minutes to react. After completion of dropping, hydrogen chloride gas was further introduced for 7 hours to react.
After the reaction, the composition of the obtained reaction solution other than the solvent by GC analysis was found to be 0.1% for unreacted biphenyl and 68.9% for 4,4′-bischloromethylbiphenyl.
After completion of the reaction, the resulting reaction solution was cooled to 15 ° C., 15 ml of water and 60 ml of cyclohexane were added and stirred, and 4,4′-bischloromethylbiphenyl deposited by suction filtration was separated. The obtained 4,4′-bischloromethylbiphenyl was further washed with 120 ml of methanol and then dried under reduced pressure at room temperature for 24 hours to obtain 51.1 g (yield based on biphenyl = 67.9%) of a dried product. . The GC purity of the dried product was 90.4%. When this dried product was recrystallized from cyclohexane, white crystals having a melting point of 136 to 137 ° C. and a GC purity of 99.0% were obtained.
[0020]
Example 2
In a four-necked flask with an internal volume of 300 ml equipped with a condenser, a thermometer, a gas inlet tube and a stirrer, 46.25 g (0.30 mol) of biphenyl, 21.52 g (0.66 mol) of 92 wt% paraformaldehyde, 24.5 g (0.18 mol) of 98% by weight zinc chloride and 60 g of cyclohexane were added. While stirring at 50 ° C., hydrogen chloride gas was introduced at 80 ml / min. 0.196 mol) was added dropwise over 4 hours to react. After completion of dropping, hydrogen chloride gas was further introduced for reaction for 5 hours.
After the reaction, the composition of the obtained reaction solution other than the solvent by GC analysis was found to be 0.1% for unreacted biphenyl and 64.4% for 4,4′-bischloromethylbiphenyl.
After completion of the reaction, the resulting reaction solution was cooled to 15 ° C., 50 ml of water and 60 ml of cyclohexane were added and stirred, and 4,4′-bischloromethylbiphenyl deposited by suction filtration was separated. The obtained 4,4′-bischloromethylbiphenyl was further washed with 120 ml of methanol and then dried under reduced pressure at room temperature for 24 hours to obtain 47.4 g (yield based on biphenyl = 62.9%) of a dried product. . The GC purity of the dried product was 92.2%.
[0021]
Example 3
The reaction was conducted in the same manner as in Example 2 except that the reaction temperature was 40 ° C., 10 g of acetic anhydride was added dropwise over 1 hour, and the hydrogen chloride gas blowing time after the addition was changed to 10 hours.
After completion of the reaction, the composition other than the solvent by GC analysis of the obtained reaction solution was found to be 0% for unreacted biphenyl and 63.7% for 4,4′-bischloromethylbiphenyl.
[0022]
Example 4
The reaction was conducted in the same manner as in Example 2 except that 9.45 g (0.1 mol) of acetyl chloride was used instead of acetic anhydride.
After the reaction, the composition of the obtained reaction solution other than the solvent by GC analysis was found to be 0% for unreacted biphenyl and 62.4% for 4,4′-bischloromethylbiphenyl.
[0023]
Example 5
Into a 300 ml glass autoclave equipped with a thermometer, a gas introduction pipe and a stirrer, 46.25 g (0.30 mol) of biphenyl, 21.52 g (0.66 mol) of 92 wt% paraformaldehyde, 24.5 g (0.18 mol) of 98 wt% zinc chloride and 10 g (0.098 mol) of acetic anhydride and a petroleum solvent (trade name: SHELLSOL D40 Shell) as a solvent were added and stirred at 40 ° C. After introducing hydrogen chloride gas and replacing the inside of the system with hydrogen chloride gas, the gas outlet was closed and the reaction was continued for 11 hours while maintaining the pressure at 2 Kg / cm 2 . After the reaction, the composition of the obtained reaction solution other than the solvent by GC analysis was found to be 0.1% for unreacted biphenyl and 69.2% for 4,4′-bischloromethylbiphenyl.
[0024]
Comparative Example 1
The reaction was conducted in the same manner as in Example 2 except that acetic anhydride was not added and the hydrogen chloride gas blowing time was changed to 10 hours.
The composition other than the solvent by GC analysis of the obtained reaction solution at the end of the reaction was found to be 6.1% for unreacted biphenyl and 37.4% for 4,4'-bischloromethylbiphenyl.
[0025]
【The invention's effect】
According to the production method of the present invention, 4,4′-bischloromethylbiphenyl can be produced in a short time and in a high yield with a small amount of catalyst.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP24880097A JP3845977B2 (en) | 1997-09-12 | 1997-09-12 | Method for producing 4,4'-bischloromethylbiphenyl |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24880097A JP3845977B2 (en) | 1997-09-12 | 1997-09-12 | Method for producing 4,4'-bischloromethylbiphenyl |
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| Publication Number | Publication Date |
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| JPH1180047A JPH1180047A (en) | 1999-03-23 |
| JP3845977B2 true JP3845977B2 (en) | 2006-11-15 |
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| CN101928198B (en) * | 2009-06-22 | 2014-09-03 | 上海华理生物医药有限公司 | Preparation method of high-purity 4,4'-dichloromethyl biphenyl |
| CN102267870A (en) * | 2011-07-18 | 2011-12-07 | 扬州市中宝银鹏合成材料有限公司 | Production process of 4,4'-bis(chloromethyl)-biphenyl |
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